The molten salt reactor (MSR) is one of the advanced nuclear reactors expected to be alternatives to the conventional water-cooled nuclear reactor systems. Despite many advantages of MSRs, properties of molten salts have not been sufficiently measured in previous studies. In addition, the corrosion of structural alloys by molten salt is the biggest challenge for the operation of MSRs. This study focuses on measurements of thermophysical and thermodynamic properties of fluoride salt fuels, salt purification, and the degradation of structural materials in static and flowing molten-salt fuels. For the measurements of properties, phase transition, specific heat capacity, vapor pressure, contact angle on nuclear-grade graphite, and density were measured. The methodologies for the property measurements used in this study were validated by measuring the properties of metals or salts that have been well studied. For the flow-induced corrosion tests, the salt flow with different velocities was simulated by rotating the stainless steel 316H (SS316H) specimens in molten NaF-KF-UF4 (FUNaK) contained in glassy carbon crucibles at 1073 K. Salt samples were intermittently collected to monitor concentration changes of corrosion products in the salt, and surfaces and cross-sections of post-test SS316H specimens were analyzed to study their corrosion behaviors. Different batches of FUNaK were synthesized using different methods of purification, such as thermal purification, U-metal purification, and hydrofluorination with electrochemical purification (chemical purification) to study impacts of salt purification on the corrosion of SS316H. The corrosion test of SS316H by thermally purified FUNaK showed that the Fe concentration increased at the beginning and then decreased while the Cr concentration continued increasing while the rate decreased. In addition, (Cr, Fe)7C3 layers, Cr-metal particles, and dendritic structures concentrated with Cr and Fe were observed on the glassy carbon crucible after the 2 m/s test. The U-metal purification and hydrofluorination with electrochemical purification reduced concentrations of oxygen and hydrogen in FUNaK and mitigated the corrosion of SS316H significantly. The infiltration of the fluoride fuel salts into graphite and the fluorination of graphite by the salts at different pressures and temperatures were also studied. The salt infiltration into graphite at pressures above its threshold pressure was observed, and the formation of carbon fluorides on the surface of post-test graphite specimens was identified. / Doctor of Philosophy / As conventional water-cooled nuclear power systems showed safety issues, the Generation IV International Forum was established to expedite the development of next-generation nuclear reactor systems. Among the six advanced nuclear reactors, the molten salt reactor (MSR) stands out for its remarkable technical advantages, including low operating pressures and increased efficiency resulting from higher operating temperatures compared to water-cooled nuclear systems. Despite their advantages, further studies need to be conducted to develop and operate MSRs, as properties of molten salts have not been comprehensively measured in previous studies, and the corrosion of structural materials by molten salt is a significant challenge to their operation. The corrosion of alloys by molten salt can be attributed to many different factors, and the level of impurities in salt is an important factor directly linked to corrosion. Thus, the purification of salt is imperative to mitigate the corrosion of MSRs and needs to be well studied. In this study, methodologies for measuring thermophysical and thermodynamic properties of fluoride fuel salts were developed and validated using reference data. In addition, the corrosion of stainless steel 316H (SS316H) in a flowing fuel salt was also studied. Although various corrosion tests with static molten salts have been conducted, studies on corrosion of alloys in flowing molten salt fuels containing uranium fluorides are still limited. This study addresses this gap by developing a test apparatus equipped with a rotating disk to simulate the flow of molten salt on the surface of alloy specimens. Different batches of fuel salts with varying impurity levels, especially oxygen and hydrogen, were prepared using different purification methods. These salts were then used for corrosion tests under the same conditions, such as temperature and time duration, to explore the impacts of the non-metallic impurities on the corrosion of SS316H. The findings revealed that the salts with lower levels of oxygen and hydrogen caused less corrosion of SS316H, underscoring that the purification of salt is indispensable to the mitigation of corrosion in MSRs. This study also explored interactions of molten-salt fuels with graphite which is a promising candidate for a moderator or reflector of MSRs for enhancing neutron economy for thermal nuclear reactors. A high-pressure graphite-infiltration test apparatus was developed to investigate infiltration of fluoride fuel salts into graphite and the fluorination of graphite.

Nuclear energy has gained crucial importance since it has a minor impact on climate change and greenhouse gas releases; additionally, the other energy sources are insufficient to reach the world's energy needs without nuclear energy. Another sign that the Generation IV International Forum (Kelly, Gen IV International Forum: A decade of progress through international cooperation, 2014) has pointed out is to utilize uranium resources to the maximum and recycle spent nuclear fuel through burn-up in the Generation IV reactor designs, one of which is the molten salt reactor (MSR). Therefore, the MSR can use the spent nuclear fuel as a fresh fuel when the actinides recycle. That reprocessing of spent fuel could be one of the opportunities to contribute to future nuclear energy goals. This study aims to develop a modified pyroprocessing method to prepare molten salt fuels for MSR from spent oxide nuclear fuel that was burned in light water reactors (LWRs). The process diagram illustrated as (1) spent fuel treatment, (2) chopping and voloxidation of spent oxide fuel, (3) oxide reduction of spent fuel, and then depending on the fuel structure and composition for the MSR, it continues by one or two of the following; – electrorefining, – chlorination, and – fluorination. The subject of this study focused on oxide reduction in two categories: chemical reduction and electrochemical reduction. The system designs have been optimized in calcium salts since they have high calcium metal and calcium oxide solubility. The significant results indicated that both methods would substantially reduce the solid uranium dioxide pellet. The chemical reduction will reduce the total solid pellet at 850oC in the composition of 55.73mol%CaCl2-12.37mol%CaF2-26.58mol%Ca-5.32mol%UO2 over 12 hours. The total reduction in the electrochemical test is seen at 850oC during 12 hours with a salt composition of 79mol%CaCl2-17mol%CaF2-4mol%CaO. These oxide reduction mechanisms are convenient ways to reprocess spent oxide fuel from LWRs to utilize in the MSR. Additionally, the reduced fuel is also applicable to using other next-generation reactors. The prospect of this research is the explicit comparison between chemical and electrochemical methods in calcium salts. / M.S. / Nuclear energy is a crucial energy production to meet the world’s future energy needs. The 6 (six) next-generation reactor design has been determined based on their sustainability, economic, and peaceful application for the world. One of those designs is molten salt reactors (MSRs) which have more attention due to their fuel choice. Most MSRs use the reprocessed fuel from current reactors or the fuel with the breeder blanket that creates more fuel while the reactor operates. This study aims to provide a diagram showing the various steps involved in the preparation of molten salt fuel from spent oxide fuel, which is a mainly utilized form of fuel in current and previous operations. The flowsheet’s first step is the treatment of spent fuel that releases most of the decay heat. The second step is that spent fuel chopping and voloxidation, which meets the requirements of removing gas products and cladding material from used fuel. Afterward, the spent oxide fuel reduces into its metal form chemically or electrochemically in oxide reduction. Then, the molten salt fuel could be fabricated in n one or two more steps from reduced metals: electrorefining, chlorination, or fluorination. Chlorination and fluorination pass through the specific gas components to convert the metal forms into salt. Electrorefining could be applied to arrange the composition of the reduced metal, and this stage is strongly dependent on the MSR designs; it may get eliminated due to its unnecessity. The oxide mechanisms mentioned above were examined under different design conditions to acquire a total reduction of the fuel pellet in calcium salts. The chemical reduction and electroreduction experiments have shown the reduced whole pellet at 850oC with two different salt mixtures. The design impacts of the reduction mechanism were discussed extensively between chemical and electrochemical reductions to identify the benefits and limitations.